US4605796A - Process for producing ethanol - Google Patents
Process for producing ethanol Download PDFInfo
- Publication number
- US4605796A US4605796A US06/682,335 US68233584A US4605796A US 4605796 A US4605796 A US 4605796A US 68233584 A US68233584 A US 68233584A US 4605796 A US4605796 A US 4605796A
- Authority
- US
- United States
- Prior art keywords
- cobalt
- acid
- ethanol
- methanol
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 140
- 238000000034 method Methods 0.000 title claims abstract description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 111
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 30
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 20
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 19
- 239000010941 cobalt Substances 0.000 claims abstract description 19
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000001869 cobalt compounds Chemical class 0.000 claims abstract description 13
- 150000002148 esters Chemical class 0.000 claims abstract description 9
- 150000001868 cobalt Chemical class 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 11
- 239000005711 Benzoic acid Substances 0.000 claims description 10
- 235000010233 benzoic acid Nutrition 0.000 claims description 10
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 claims description 6
- MQIKJSYMMJWAMP-UHFFFAOYSA-N dicobalt octacarbonyl Chemical group [Co+2].[Co+2].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] MQIKJSYMMJWAMP-UHFFFAOYSA-N 0.000 claims description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 4
- GPSDUZXPYCFOSQ-UHFFFAOYSA-N m-toluic acid Chemical compound CC1=CC=CC(C(O)=O)=C1 GPSDUZXPYCFOSQ-UHFFFAOYSA-N 0.000 claims description 4
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 claims description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 2
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 2
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 2
- OBWXQDHWLMJOOD-UHFFFAOYSA-H cobalt(2+);dicarbonate;dihydroxide;hydrate Chemical compound O.[OH-].[OH-].[Co+2].[Co+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O OBWXQDHWLMJOOD-UHFFFAOYSA-H 0.000 claims description 2
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 2
- ILZSSCVGGYJLOG-UHFFFAOYSA-N cobaltocene Chemical compound [Co+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 ILZSSCVGGYJLOG-UHFFFAOYSA-N 0.000 claims description 2
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 claims description 2
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 claims description 2
- WXAZIUYTQHYBFW-UHFFFAOYSA-N tris(4-methylphenyl)phosphane Chemical compound C1=CC(C)=CC=C1P(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 WXAZIUYTQHYBFW-UHFFFAOYSA-N 0.000 claims description 2
- BWLBGMIXKSTLSX-UHFFFAOYSA-N 2-hydroxyisobutyric acid Chemical compound CC(C)(O)C(O)=O BWLBGMIXKSTLSX-UHFFFAOYSA-N 0.000 claims 1
- 125000003944 tolyl group Chemical group 0.000 claims 1
- 239000006227 byproduct Substances 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 230000009257 reactivity Effects 0.000 description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 13
- 239000002253 acid Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 239000003446 ligand Substances 0.000 description 12
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 8
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 8
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 7
- 229910052740 iodine Inorganic materials 0.000 description 7
- 239000011630 iodine Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- -1 cobalt organic acid salt Chemical class 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 5
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- 229910052787 antimony Inorganic materials 0.000 description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical group [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 4
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical group [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 150000002170 ethers Chemical class 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 229910052707 ruthenium Inorganic materials 0.000 description 4
- CMTOAZYCDKAFHL-UHFFFAOYSA-N CC1=CC=CC=C1.CC1=CC=CC=C1.CC1=CC=CC=C1 Chemical compound CC1=CC=CC=C1.CC1=CC=CC=C1.CC1=CC=CC=C1 CMTOAZYCDKAFHL-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- IRFULBOCZHZKIX-UHFFFAOYSA-N [Co].[I] Chemical compound [Co].[I] IRFULBOCZHZKIX-UHFFFAOYSA-N 0.000 description 2
- KUJLLNAUIKQKND-UHFFFAOYSA-N [I].[Ru].[Co] Chemical compound [I].[Ru].[Co] KUJLLNAUIKQKND-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 150000003304 ruthenium compounds Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- BCJVBDBJSMFBRW-UHFFFAOYSA-N 4-diphenylphosphanylbutyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCCP(C=1C=CC=CC=1)C1=CC=CC=C1 BCJVBDBJSMFBRW-UHFFFAOYSA-N 0.000 description 1
- JRLTTZUODKEYDH-UHFFFAOYSA-N 8-methylquinoline Chemical group C1=CN=C2C(C)=CC=CC2=C1 JRLTTZUODKEYDH-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- PMHCSCQXRLVFNR-UHFFFAOYSA-N [Br].[Co] Chemical compound [Br].[Co] PMHCSCQXRLVFNR-UHFFFAOYSA-N 0.000 description 1
- FONFJFUBWWRBKA-UHFFFAOYSA-N [N].[I] Chemical compound [N].[I] FONFJFUBWWRBKA-UHFFFAOYSA-N 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- WXBLLCUINBKULX-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1 WXBLLCUINBKULX-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- HAHDAHKRCJXVAP-UHFFFAOYSA-N carbanide;cobalt Chemical compound [CH3-].[Co] HAHDAHKRCJXVAP-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- RHFOYRRUVLOOJP-UHFFFAOYSA-N ethoxyethane;propanoic acid Chemical compound CCOCC.CCC(O)=O RHFOYRRUVLOOJP-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012527 feed solution Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical group I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 150000002497 iodine compounds Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000003003 phosphines Chemical group 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof
Definitions
- This invention relates to a process for producing ethanol from methanol, carbon monoxide and hydrogen selectively.
- ethanol was produced from methanol, carbon monoxide and hydrogen by using a catalyst comprising a cobalt component and an iodine or bromine component and optionally a ruthenium component, an osmium component and a ligand.
- a catalyst comprising a cobalt component and an iodine or bromine component and optionally a ruthenium component, an osmium component and a ligand.
- Japanese Patent Publication (kokoku) No. 24863/1963 discloses a process for producing ethanol which comprises reacting methanol, carbon monoxide and hydrogen in the presence of a cobalt catalyst and an iodine co-catalyst.
- 3,285,948 discloses a process for producing ethanol which comprises reacting methanol, carbon monoxide and hydrogen in the presence of a catalyst comprising a soluble cobalt compound, iodine or an iodine compound and a ruthenium compound.
- Japanese Patent Publication (kokai) No. 147009/1978 discloses a process for producing ethanol which comprises reacting methanol, carbon monoxide and hydrogen in the presence of a cobalt catalyst, an iodine or bromine and an organic phosphorus compound co-catalyst and a large amount of monocarboxylic acid or derivatives thereof.
- a cobalt catalyst an iodine or bromine and an organic phosphorus compound co-catalyst
- monocarboxylic acid or derivatives thereof forms an ester with the ethanol produced by the reaction or the methanol which is a starting material; and the use of large amount of such acid lowers the selectivity to neat ethanol.
- the resulting complex composition of the reaction mixture makes the recovering process for ethanol complicated.
- Japanese Patent Publication (kokai) No. 49326/1980 discloses a multidentate ligand containing cobalt-bromine or iodine-nitrogen or phosphorus atom as such catalyst.
- British Pat. No. 2,036,739 discloses a process for producing ethanol by reacting methanol, carbon monoxide and hydrogen in the presence of a catalyst composed of cobalt and a metal of Group VIII of the Periodic Table (Fe, Ru, Os, Rh, Ir, Ni, Pd and Pt), promoter composed of a tertiary phosphine, a tertiary arsine or a tertiary antimony and iodide or bromine.
- a catalyst composed of cobalt and a metal of Group VIII of the Periodic Table (Fe, Ru, Os, Rh, Ir, Ni, Pd and Pt)
- promoter composed of a tertiary phosphine, a tertiary arsine or a tertiary antimony and iodide or bromine.
- Japanese Patent Publication (kokai) No. 92330/1980 discloses a catalyst comprising hydride cobalt carbonyl complex, iodine, a ruthenium compound and a tertiary phosphine, a tertiary antimony or a tertiary arsine as such catalyst.
- 4,233,466 discloses a catalyst for production of ethanol from methanol, carbon monoxide and hydrogen which comprises cobalt, ruthenium, iodine and a tertiary phosphine in which a molar ratio of phosphorus to iodine is between 1:0.36-1:5 and a molar ratio of phosphorus to cobalt is more than 1.5.
- Japanese Patent Publication (kokoku) No. 24863/1963 or U.S. Pat. No. 3,285,948 discloses a process for producing ethanol which comprises reacting methanol, carbon monoxide and hydrogen at a temperature of 175°-230° C. and a pressure of more than 281 Kg/cm 2 G in the presence of a catalyst comprising cobalt-iodine or a catalyst comprising cobalt-iodine-ruthenium and in the absence of any solvent. Since the catalysts do not contain any ligands, it is easy to handle them. However, when the above catalysts are used, by-products, such as ethers and methyl acetate are formed in a large amount, so selectivity to neat ethanol becomes lower extremely.
- the catalysts contain cobalt and ruthenium as well as iodine or bromine and ligands, such as a tertiary phosphine, a tertiary antimony or a tertiary arsine as a ligand, so the following shortcomings are produced in case of carrying out the reaction in the presence of the catalyst on a commercial base:
- ligands such as a tertiary phosphine are instable to heat, the ligands are likely to be decomposed in the reaction system, or quality of the ligands is likely to be changed. Therefore, it is difficult to recover the active catalysts from the system. In addition, recovery of each component constituting the catalysts not only need complicated operation, but also loss of the catalysts is great in recovery of the catalysts. Since the catalysts are costly, loss of the catalysts is unpreferablly in case of recovering the catalysts.
- the present inventors carried out research for overcoming the shortcomings mentioned above. As a result, we found that when methanol reacts with carbon monoxide and hydrogen in the presence of (a) a catalyst containing a cobalt component and a tertiary phosphine and (b) small amount of a promoter comprising an aromatic carboxylic acid, an ester thereof or a cobalt salt of aromatic carboxylic acid, ethanol is produced in high selectivity to ethanol and in high reaction rate.
- This invention relates to a process for producing ethanol which comprises reacting methanol, carbon monoxide and hydrogen in the presence of (a) a catalyst comprising cobalt or a cobalt compound and a tertiary phosphine as an effective component and (b) a promoter comprising an aromatic carboxylic acid, an ester thereof, or a cobalt salt of aromatic carboxylic acid.
- the cobalt compounds employed in the practice of this invention include, for example, cobalt carbonyls, such as dicobalt octacarbonyl and cobalt hydride tetracarbonyl, an inorganic cobalt compound, such as cobalt hydroxide, cobalt carbonate or basic cobalt carbonate, an organic cobalt compound, such as a cobalt organic acid salt, cobaltocene or cobalt acetyl acetonate, or other cobalt compounds which produce cobalt carbonyl in the reaction system.
- the cobalt compound may be used alone or as a mixture. Dicobalt octacarbonyl is preferable.
- the amount of the cobalt compound employed is in the range of 1-300 mg-atom, preferably 5-100 mg-atom in terms of cobalt per 1 mol of methanol.
- the amount of cobalt compound is less than the lower limit mentioned above, though the reaction proceeds, the reaction rate is lowered.
- the use of cobalt compound in an amount of more than the upper limit merely adds to production cost.
- the tertiary phosphines of the present invention include, for example, tri-n-butyl phosphine, triphenyl phosphine, tri-p-tolylphosphine, tricyclohexyl phosphine, bis(1,4-diphenyl phosphino)butane and bis(1,6-diphenyl phosphino)hexane.
- Tri-n-butyl phosphine is preferable.
- the amount of the tertiary phosphine may be employed so that the atomic ratio of cobalt to phosphorus is in the range of 1:0.1 to 1:3, preferably 1:0.5 to 1:2.5.
- the use of the tertiary phosphine in an amount of less than the lower limit is less effective for suppressing formation of esters or ethers.
- the use of tertiary phosphine in an amount of more than the upper limit lowers the reaction rate.
- the aromatic carboxylic acids employed in the practice of this invention include monocarboxylic acids, such as, for example, benzoic acid, o-toluic acid, m-toluic acid and p-toluic acid; polycarboxylic acids, such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid and trimesic acid; or esters or cobalt salts of these acids.
- the amount of the acid, ester or cobalt salt of the acid employed may be in the range of 0.5-30 milli mol, preferably 1-15 milli mol per 1 mol of methanol.
- the use of the promoter in an amount of less than the lower limit does not sufficiently promote the reaction.
- the use of the promoter in an amount of more than the upper limit lowers selectivity to neat ethanol as well as selectivity to realizable ethanol.
- aliphatic acids such as formic acid, and acetic acid or the esters or cobalt salts thereof are used in place of the promoter, the aliphatic acids do not increase the reaction rate and the selectivity to ethanol.
- solvent is not critical in this invention. However, it is preferable that the reaction is carried out in the presence of solvents which do not give a bad effect on the reaction.
- the solvents which are inert to the reaction system include hydrocarbons and ethers.
- Hydrocarbon solvents include, for example, aromatic hydrocarbons, such as toluene, benzene and xylene; aliphatic hydrocarbons, such as hexane and octane; and alicyclic hydrocarbons, such as cyclohexane.
- the ether solvents include, for example, diethyl ether, diiopropyl ether, dioxane and tetrahydrofuran. Toluene is preferable.
- the amount of the solvent employed may be in the range of 0.1-10 mol, preferably 0.2-5 mol per 1 mol of methanol. Use of solvent in an amount of more than the above upper limit lowers the space time yield of ethanol and is not practical.
- the reaction temperature depends on the catalyst employed and other reaction conditions. In general, the temperature may be in the range of 150°-300° C., preferably 200°-260° C. Though the reaction proceeds at a temperature below 150° C., the reaction rate is low; at temperature above 300° C. by-products forms.
- the reaction pressure may be in the range of more than 50 Kg/cm 2 , and preferably, the pressure is in the range of 100-500 Kg/cm 2 in the practice of the present invention.
- Carbon monoxide and hydrogen may be used in an amount of more than the stoichiometric amount of methanol.
- the molar ratio of CO to H 2 employed may be in the range of 4:1 to 1:4, preferably 2:1 to 1:3.
- Carbon monoxide and hydrogen employed in the present invention may contain argon, nitrogen, carbon dioxide, methane, ethane and other inert gases. In this case, the total partial pressure of each of carbon monoxide and hydrogen is within the above reaction pressure.
- the present invention can be carried out either as batch process or as a continuous process.
- the present invention is further illustrated by non-limiting Examples and Control tests.
- Example 1 The procedures of Example 1 were repeated except that benzoic acid was employed in amounts as shown in Table 1. The results are shown in Table 1.
- Example 2 The procedures of Example 1 were repeated that the catalysts and promoters were employed in amounts as shown in Table 2. The reaction conditions are also shown in Table 2.
- Example 1 The procedure of Example 1 was repeated except that benzoic acid was not employed. The results are shown in the following:
- Example 1 The procedures of Example 1 were repeated except that the components were employed in amounts as shown in Table 3.
- the reaction solution contained 16.2% of methanol, 18.0% of ethanol, 0.3% of acetaldehyde, 0.54% of methyl formate, 0.25% of diethyl ether, 0.1% of methyl acetate and 0.72% of propanol. This corresponds to reactivity of methanol of 47.5% and selectivity to neat ethanol of 85.5%; this shows substantial reactivity of methanol of 46.4% and selectivity of realizable ethanol of 90.5%.
Abstract
Description
______________________________________ methyl formate 11.70% methyl ethyl ether 1.10% methyl acetate 2.35% acetaldehyde 0.66% ______________________________________
TABLE 1 ______________________________________ Experiment No. 1* 2 3 4 5 6 7 8 ______________________________________ Amount of benzoic acid 0 1 2 3 5 8 15 20 employed per 1 mol of CH.sub.3 OH (milli mol) Selectivity to 53.6 56 63 68 71 70 51 40 ethanol (%) Selectivity to 68.1 72 76 80 84 83 74 66 realizable ethanol (%) ______________________________________ *The data are the ones of Control Test 1.
TABLE 2 __________________________________________________________________________ Example 3 4 5 6 7 8 9 __________________________________________________________________________ methanol g (mol) 10 6 10 10 10 10 10 (0.3121) (0.1873) (0.3121) (0.3121) (0.3121) (0.3121) (0.3121) Co.sub.2 (CO).sub.8 g (mol) 2 2 2 2 2 2 2 (0.0058) (0.0058) (0.0058) (0.0058) (0.0058) (0.0058) (0.0058) promoter benzoic benzoic p-toluic terephthalic methyl cobalt benzoic g (milli mol) acid acid acid acid benzoate benzoate acid 0.20 0.20 0.22 0.27 0.22 0.25 0.30 (1.64) (1.64) (1.62) (1.63) (1.62) (0.83) (2.46) tri-n-butyl 3 3 3 3 3 3 3 phosphine g (mol) (0.0148) (0.0148) (0.0148) (0.0148) (0.0148) (0.0148) (0.0148) solvent g (mol) toluene toluene toluene toluene toluene toluene 1,4-dioxane 10 10 10 10 10 10 10 (0.109) (0.109) (0.109) (0.109) (0.109) (0.109) (0.113) reaction 225-230 225-230 225-230 225-230 225-230 225-230 225-230 temperature °C. reaction time hr 3.0 1.5 1.5 1.5 1.5 1.5 1.5 reactivity of 38.6 52.3 22.5 20.9 22.4 24.3 29.7 CH.sub.3 OH (substan- (37.0) (51.7) (19.7) (18.8) (19.9) (22.4) (29.2) tial reactivity of CH.sub.3 OH) selectivity to each compound % ethanol 76.1 70.5 71.3 71.1 74.7 71.4 72.8 methyl 2.67 0.40 10.5 8.11 9.15 6.11 1.31 formate methyl 0.95 0.23 2.41 2.02 2.23 1.01 0.50 acetate methyl ethyl 1.72 1.82 1.55 1.11 1.70 2.05 1.86 ether acetaldehyde 0.25 0.22 0.53 0.66 0.53 0.38 0.16 realizable 80.6 72.6 83.0 80.4 85.7 79.0 75.2 ethanol __________________________________________________________________________
______________________________________ reactivity of methanol 15.0% selectivity to neat ethanol 53.6% selectivity to methyl formate 17.8% selectivity to methyl acetate 1.81% selectivity to methyl ethyl ether 1.86% selectivity to acetaldehyde 1.02% ______________________________________
TABLE 3 ______________________________________ Control Test No. 2 3 4 5 ______________________________________ methanol g (mol) 10 10 10 13 (0.3121) (0.3121) (0.3121) (0.4057) Co.sub.2 (CO).sub.8 g (mol) 2 2 2 cobalt acetate (0.0058) (0.0058) (0.0058) tetrahydrate 1.25 (0.0050) promotor -- benzoic acetic propionic g (milli mol) acid acid acid 0.20 0.10 15 (1.64) (1.67) (203) tri-n-butyl 3 -- 3 -- phosphine g (mol) (0.0148) (0.0148) solvent g (mol) toluene toluene toluene -- 10 10 10 -- (0.109) (0.109) (0.109) reaction 225-230 225-230 225-230 180-185 temperature °C. reaction time hr 3.0 1.5 1.5 8 reactivity of 28.7 9.10 17.9 67.3 CH.sub.3 OH (substan- (26.3) (7.11) (17.1) (33.9) tial reactivity of CH.sub.3 OH) % reactivity to each compound % ethanol 56.3 23.4 54.8 19.5 methyl 7.00 18.00 2.68 0.26 formate methyl 0.61 1.41 0.50 8.72 acetate methyl ethyl 2.70 6.53 2.78 ethyl ether propionate 11.3 acetaldehyde -- -- 0.42 0.48 realizable 62.9 33.8 59.0 64.5 ethanol ______________________________________
Claims (9)
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JP58244172A JPS60136525A (en) | 1983-12-26 | 1983-12-26 | Production of ethanol |
JP58-244172 | 1983-12-26 |
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US06/682,335 Expired - Fee Related US4605796A (en) | 1983-12-26 | 1984-12-17 | Process for producing ethanol |
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Also Published As
Publication number | Publication date |
---|---|
CA1231723A (en) | 1988-01-19 |
JPS6114138B2 (en) | 1986-04-17 |
JPS60136525A (en) | 1985-07-20 |
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